# US 9,751,966 B2 · Rapid cure polymeric resins

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- Number: US 9,751,966 B2
- Document ID: US9751966B2
- Status: Granted
- Kind: B2
- Application number: 14/924,079
- Filed: 2015-10-27
- Published: 2016-06-23
- Granted: 2017-09-05
- Earliest claimed: 2014-12-22
- Assignees: The Boeing Company
- Applicants: The Boeing Company
- Inventors: Andrew M. Zweig
- Web page: https://patentgrep.com/patent/US9751966B2

## CPC

- C08F 212/34: Monomers containing two or more unsaturated aliphatic radicals
- C07C 323/12: the carbon skeleton being acyclic and saturated
- C08F 12/22: Oxygen
- C08F 12/30: Sulfur
- C08F 12/34: Monomers containing two or more unsaturated aliphatic radicals
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

A polysulfide material having reactive vinyl end groups and a method of making a vinyl end-capped polysulfide material are described. The vinyl end-capped polysulfide material has potential applications as a sealant, an adhesive, a coating, a caulking, or the like. In a specific example, the polysulfide material may be used as a precursor material for a sealant resin in the manufacturing of an integral fuel tank of an aircraft. An example method for making polysulfide materials includes contacting a vinyl-functionalized aryl halide and/or a vinyl-functionalized heteroaryl halide with dithiols and/or trithiols in the presence of an organic solvent.

## Claims

### Claim 1

A polymer of formula (I):
wherein:
each instance of R1 is -alkyl-O-alkyl-O-alkyl-;
each instance of R2 is the same or different and is selected from
each instance of R24 is the same or different and is selected from hydrogen (H), alkyl, or alkoxy;
“Linker” is of formula (II):
c is less than 1.0;
d is 0 when c is 0; and
a+b+d is from about 7 to about 38.

### Claim 2 (depends on 1)

The polymer of claim 1, wherein each instance of R2 is the same or different and is selected from -aryl-alkyl- or -aryl-.

### Claim 3 (depends on 2)

The polymer of claim 2, wherein each instance of R2 is the same or different and is selected from -benzyl- or -phenyl-.

### Claim 4 (depends on 3)

The polymer of claim 3, wherein each instance of R1 is -ethyl-O-methyl-O-ethyl-.

### Claim 5 (depends on 1)

The polymer of claim 1, wherein each instance of R2 is -heteroaryl-.

### Claim 6 (depends on 1)

The polymer of claim 1, wherein each instance of R2 is -heteroaryl-alkyl-.

### Claim 7 (depends on 1)

The polymer of claim 1, wherein each instance of -alkyl- of R1 is selected from the group consisting of -methyl-, -ethyl-, and -propyl-.

### Claim 8 (depends on 1)

The polymer of claim 1, wherein c is greater than 0 and the Linker of formula (I) is:

### Claim 9 (depends on 8)

The polymer of claim 8, wherein each instance of R1 is -ethyl-O-methyl-O-ethyl- and each instance of R2 is -benzyl-.

### Claim 10 (depends on 8)

The polymer of claim 8, wherein each instance of -alkyl- of R1 is selected from the group consisting of -methyl-, -ethyl-, and -propyl-.

### Claim 11 (depends on 1)

The polymer of claim 1, wherein c=0, and the polymer of formula (I) is selected from the group consisting of:
Ex.
R2
R1
1a
—ethyl—O—methyl—O—ethyl—
2a
—ethyl—O—methyl—O—ethyl—
3a
—ethyl—O—methyl—O—ethyl—
4a
—ethyl—O—methyl—O—ethyl—
5a
—ethyl—O—methyl—O—ethyl—
6a
—ethyl—O—methyl—O—ethyl—
7a
—ethyl—O—methyl—O—ethyl—
8a
—ethyl—O—methyl—O—ethyl—
9a
—ethyl—O—methyl—O—ethyl—
10a
—ethyl—O—methyl—O—ethyl—
11a
—ethyl—O—methyl—O—ethyl—
12a
—ethyl—O—methyl—O—ethyl—
13a
—ethyl—O—methyl—O—ethyl—
14a
—ethyl—O—methyl—O—ethyl—
15a
—ethyl—O—methyl—O—ethyl—
16a
—ethyl—O—methyl—O—ethyl—
17a
—ethyl—O—methyl—O—ethyl—
18a
—ethyl—O—methyl—O—ethyl—
19a
—ethyl—O—methyl—O—ethyl—
20a
—ethyl—O—methyl—O—ethyl—
21a
—ethyl—O—methyl—O—ethyl—
22a
—ethyl—O—methyl—O—ethyl—
23a
—ethyl—O—methyl—O—ethyl—
24a
—ethyl—O—methyl—O—ethyl—
25a
—ethyl—O—methyl—O—ethyl—
26a
—methyl—O—methyl—O—methyl—
27a
—methyl—O—methyl—O—methyl—
28a
—ethyl—O—ethyl—O—ethyl—
29a
—ethyl—O—ethyl—O—ethyl—
30a
—methyl—O—ethyl—O—methyl—
31a
—methyl—O—ethyl—O—methyl—
32a
—methyl—O—ethyl—O—methyl—
33a
—propyl—O—methyl—O—propyl—
34a
—propyl—O—methyl—O—propyl—
35a
—propyl—O—methyl—O—propyl—
36a
—ethyl—O—propyl—O—ethyl—
37a
—ethyl—O—propyl—O—ethyl—
38a
—propyl—O—methyl—O—propyl—
39a
—propyl—O—methyl—O—propyl—
40a
—propyl—O—methyl—O—propyl—
41a
—ethyl—O—propyl—O—ethyl—
42a
—ethyl—O—propyl—O—ethyl—
43a
—propyl—O—methyl—O—propyl—
44a
—ethyl—O—propyl—O—ethyl—
45a
—ethyl—O—propyl—O—ethyl—
46a
—ethyl—O—propyl—O—ethyl—
47a
—propyl—O—methyl—O—propyl—
48a
—ethyl—O—propyl—O—ethyl—
49a
—ethyl—O—ethyl—O—ethyl—
50a
—ethyl—O—propyl—O—ethyl—.

### Claim 12 (depends on 1)

The polymer of claim 1, wherein c is greater than 0 and the polymer of formula (I) is selected from the group consisting of:
Ex.
Linker
R2
R1
1b
—ethyl—O—methyl—O—ethyl—
2b
—ethyl—O—methyl—O—ethyl—
3b
—ethyl—O—methyl—O—ethyl—
4b
—ethyl—O—methyl—O—ethyl—
5b
—ethyl—O—methyl—O—ethyl—
6b
—ethyl—O—methyl—O—ethyl—
7b
—ethyl—O—methyl—O—ethyl—
8b
—ethyl—O—methyl—O—ethyl—
9b
—ethyl—O—methyl—O—ethyl—
10b
—ethyl—O—methyl—O—ethyl—
11b
—ethyl—O—methyl—O—ethyl—
12b
—ethyl—O—methyl—O—ethyl—
13b
—ethyl—O—methyl—O—ethyl—
14b
—ethyl—O—methyl—O—ethyl—
15b
—ethyl—O—methyl—O—ethyl—
16b
—ethyl—O—methyl—O—ethyl—
17b
—ethyl—O—methyl—O—ethyl—
18b
—ethyl—O—methyl—O—ethyl—
19b
—ethyl—O—methyl—O—ethyl—
20b
—ethyl—O—methyl—O—ethyl—
21b
—ethyl—O—methyl—O—ethyl—
22b
—ethyl—O—methyl—O—ethyl—
23b
—ethyl—O—methyl—O—ethyl—
24b
—ethyl—O—methyl—O—ethyl—
25b
—ethyl—O—methyl—O—ethyl—
26b
—methyl—O—methyl—O—methyl—
27b
—methyl—O—methyl—O—methyl—
28b
—ethyl—O—ethyl—O—ethyl—
29b
—ethyl—O—ethyl—O—ethyl—
30b
—methyl—O—ethyl—O—methyl—
31b
—methyl—O—ethyl—O—methyl—
32b
—methyl—O—ethyl—O—methyl—
33b
—propyl—O—methyl—O—propyl—
34b
—propyl—O—methyl—O—propyl—
35b
—propyl—O—methyl—O—propyl—
36b
—ethyl—O—propyl—O—ethyl—
37b
—ethyl—O—propyl—O—ethyl—
38b
—propyl—O—methyl—O—propyl—
39b
—propyl—O—methyl—O—propyl—
40b
—propyl—O—methyl—O—propyl—
41b
—ethyl—O—propyl—O—ethyl—
42b
—ethyl—O—propyl—O—ethyl—
43b
—propyl—O—methyl—O—propyl—
44b
—ethyl—O—propyl—O—ethyl—
45b
—ethyl—O—propyl—O—ethyl—
46b
—ethyl—O—propyl—O—ethyl—
47b
—propyl—O—methyl—O—propyl—
48b
—ethyl—O—propyl—O—ethyl—
49b
—ethyl—O—ethyl—O—ethyl—
50b
—ethyl—O—propyl—O—ethyl—.

### Claim 13

A method of making a polymer, comprising:
contacting, in presence of an organic solvent, at least one compound of formula (III):
at least one compound of formula (IV):
and
at least one compound of formula (V):
wherein:
each instance of R1 is -alkyl-O-alkyl-O-alkyl-;
each instance of R2 is the same or different and is selected from
each instance of R24 is the same or different and is selected from hydrogen (H), alkyl, or alkoxy;
X is halo;
n is from about 7 to about 38; and
e+f+g is from about 7 to about 38.

### Claim 14 (depends on 13)

The method of claim 13, wherein X is chlorine, R2 is -benzyl-, and at least one instance of R1 is -ethyl-O-methyl-O-ethyl-.

### Claim 15 (depends on 13)

The method of claim 13, wherein the organic solvent is N,N-dimethylformamide.

### Claim 16

A polymer blend comprising:
a first polymer of formula (I):
wherein:
R1 is -alkyl-O-alkyl-O-alkyl-,
each instance of R2 is the same or different and is selected from
each instance of R24 is the same or different and is selected from hydrogen (H), alkyl, or alkoxy;
“Linker” is of formula (II):
c is less than 1.0 but greater than 0, and
a+b+d is from about 7 to about 38; and
a second polymer of formula (I):
wherein:
R1 is -alkyl-O-alkyl-O-alkyl-,
each instance of R2 is the same or different and is selected from
each instance of R24 is the same or different and is selected from hydrogen (H), alkyl, or alkoxy;
“Linker” is of formula (II):
c=0, d=0, and
a+b is from about 7 to about 38.

### Claim 17 (depends on 16)

The polymer blend of claim 16, wherein the first polymer of formula (I) is:
wherein:
n ranges from about 7 to about 38,
each instance of R24 is the same or different and is selected from H, alkyl, or alkoxy; and
wherein the second polymer of formula (I) is:
wherein:
e+f+g ranges from about 7 to about 38, and
each instance of R24 is the same or different and is selected from H, alkyl, or alkoxy.

### Claim 18 (depends on 16)

The polymer blend of claim 16, wherein ‘c’ is greater than 0 and the first polymer of formula (I) is selected from the group consisting of:
Ex.
Linker
R2
R1
1b
—ethyl—O—methyl—O—ethyl—
2b
—ethyl—O—methyl—O—ethyl—
3b
—ethyl—O—methyl—O—ethyl—
4b
—ethyl—O—methyl—O—ethyl—
5b
—ethyl—O—methyl—O—ethyl—
6b
—ethyl—O—methyl—O—ethyl—
7b
—ethyl—O—methyl—O—ethyl—
8b
—ethyl—O—methyl—O—ethyl—
9b
—ethyl—O—methyl—O—ethyl—
10b
—ethyl—O—methyl—O—ethyl—
11b
—ethyl—O—methyl—O—ethyl—
12b
—ethyl—O—methyl—O—ethyl—
13b
—ethyl—O—methyl—O—ethyl—
14b
—ethyl—O—methyl—O—ethyl—
15b
—ethyl—O—methyl—O—ethyl—
16b
—ethyl—O—methyl—O—ethyl—
17b
—ethyl—O—methyl—O—ethyl—
18b
—ethyl—O—methyl—O—ethyl—
19b
—ethyl—O—methyl—O—ethyl—
20b
—ethyl—O—methyl—O—ethyl—
21b
—ethyl—O—methyl—O—ethyl—
22b
—ethyl—O—methyl—O—ethyl—
23b
—ethyl—O—methyl—O—ethyl—
24b
—ethyl—O—methyl—O—ethyl—
25b
—ethyl—O—methyl—O—ethyl—
26b
—methyl—O—methyl—O—methyl—
27b
—methyl—O—methyl—O—methyl—
28b
—ethyl—O—ethyl—O—ethyl—
29b
—ethyl—O—ethyl—O—ethyl—
30b
—methyl—O—ethyl—O—methyl—
31b
—methyl—O—ethyl—O—methyl—
32b
—methyl—O—ethyl—O—methyl—
33b
—propyl—O—methyl—O—propyl—
34b
—propyl—O—methyl—O—propyl—
35b
—propyl—O—methyl—O—propyl—
36b
—ethyl—O—propyl—O—ethyl—
37b
—ethyl—O—propyl—O—ethyl—
38b
—propyl—O—methyl—O—propyl—
39b
—propyl—O—methyl—O—propyl—
40b
—propyl—O—methyl—O—propyl—
4lb
—ethyl—O—propyl—O—ethyl—
42b
—ethyl—O—propyl—O—ethyl—
43b
—propyl—O—methyl—O—propyl—
44b
—ethyl—O—propyl—O—ethyl—
45b
—ethyl—O—propyl—O—ethyl—
46b
—ethyl—O—propyl—O—ethyl—
47b
—propyl—O—methyl—O—propyl—
48b
—ethyl—O—propyl—O—ethyl—
49b
—ethyl—O—ethyl—O—ethyl—
50b
—ethyl—O—propyl—O—ethyl—.

### Claim 19 (depends on 16)

The polymer blend of claim 16, wherein ‘c’ is 0 and the second polymer of formula (I) is selected from the group consisting of:
Ex.
R2
R1
1a
—ethyl—O—methyl—O—ethyl—
2a
—ethyl—O—methyl—O—ethyl—
3a
—ethyl—O—methyl—O—ethyl—
4a
—ethyl—O—methyl—O—ethyl—
5a
—ethyl—O—methyl—O—ethyl—
6a
—ethyl—O—methyl—O—ethyl—
7a
—ethyl—O—methyl—O—ethyl—
8a
—ethyl—O—methyl—O—ethyl—
9a
—ethyl—O—methyl—O—ethyl—
10a
—ethyl—O—methyl—O—ethyl—
11a
—ethyl—O—methyl—O—ethyl—
12a
—ethyl—O—methyl—O—ethyl—
13a
—ethyl—O—methyl—O—ethyl—
14a
—ethyl—O—methyl—O—ethyl—
15a
—ethyl—O—methyl—O—ethyl—
16a
—ethyl—O—methyl—O—ethyl—
17a
—ethyl—O—methyl—O—ethyl—
18a
—ethyl—O—methyl—O—ethyl—
19a
—ethyl—O—methyl—O—ethyl—
20a
—ethyl—O—methyl—O—ethyl—
21a
—ethyl—O—methyl—O—ethyl—
22a
—ethyl—O—methyl—O—ethyl—
23a
—ethyl—O—methyl—O—ethyl—
24a
—ethyl—O—methyl—O—ethyl—
25a
—ethyl—O—methyl—O—ethyl—
26a
—methyl—O—methyl—O—methyl—
27a
—methyl—O—methyl—O—methyl—
28a
—ethyl—O—ethyl—O—ethyl—
29a
—ethyl—O—ethyl—O—ethyl—
30a
—methyl—O—ethyl—O—methyl—
31a
—methyl—O—ethyl—O—methyl—
32a
—methyl—O—ethyl—O—methyl—
33a
—propyl—O—methyl—O—propyl—
34a
—propyl—O—methyl—O—propyl—
35a
—propyl—O—methyl—O—propyl—
36a
—ethyl—O—propyl—O—ethyl—
37a
—ethyl—O—propyl—O—ethyl—
38a
—propyl—O—methyl—O—propyl—
39a
—propyl—O—methyl—O—propyl—
40a
—propyl—O—methyl—O—propyl—
41a
—ethyl—O—propyl—O—ethyl—
42a
—ethyl—O—propyl—O—ethyl—
43a
—propyl—O—methyl—O—propyl—
44a
—ethyl—O—propyl—O—ethyl—
45a
—ethyl—O—propyl—O—ethyl—
46a
—ethyl—O—propyl—O—ethyl—
47a
—propyl—O—methyl—O—propyl—
48a
—ethyl—O—propyl—O—ethyl—
49a
—ethyl—O—ethyl—O—ethyl—
50a
—ethyl—O—propyl—O—ethyl—.